US2020056054A1PendingUtilityA1

Multi-scale block copolymer coating that induces hydrophobic properties

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Assignee: MASSACHUSETTS INST TECHNOLOGYPriority: Dec 2, 2016Filed: Nov 29, 2017Published: Feb 20, 2020
Est. expiryDec 2, 2036(~10.3 yrs left)· nominal 20-yr term from priority
Inventors:Mukarram Ahmad TahirKarim GadelrabYi DingLi-Chen ChengCaroline A, RossAlfredo Alexander-Katz
B32B 5/22B32B 2307/50B32B 2255/02B32B 5/022B32B 2255/20C03C 2218/33B32B 9/007B32B 25/10B32B 27/28C03C 2217/76B32B 2255/28C09D 153/00C09D 183/10B32B 2437/00B32B 27/12B32B 25/14B32B 2307/412B32B 9/047B32B 5/024C03C 17/42B32B 2307/732B32B 2307/73B32B 2605/00B32B 2551/00B32B 2255/12B32B 29/02B32B 27/322B32B 27/308C03C 17/3405B32B 2255/26B32B 27/36B32B 2307/754B32B 27/32B32B 2307/538B32B 27/40B32B 2457/20B32B 5/26B32B 2255/10B32B 9/005B32B 2457/12B32B 27/34B32B 27/30C09D 5/002B32B 17/10
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Claims

Abstract

Disclosed are methods of coating a surface of a substrate with a hydrophobic layer based on iterative steps of spin-coating, annealing, and etching of block copolymer thin films into multi-layer nano-meshes. Also disclosed are articles comprising a surface with a polymer coating, and methods of using the same as a self-cleaning surface.

Claims

exact text as granted — not AI-modified
1 . A method of coating a surface of a substrate, comprising the steps of:
 (a) providing a substrate;   (b) coating the substrate with a first block copolymer;   (c) annealing the first block copolymer on the surface;   (d) etching the first block copolymer by a first etching technique, thereby producing a first patterned block copolymer;   (e) further coating the first patterned block copolymer with a second block copolymer;   (f) annealing the second block copolymer;   (g) etching the second block copolymer by a second etching technique, thereby producing a second patterned block copolymer;   (h) optionally repeating cycles comprising steps (e), (f), and (g); and   (i) passivating the coating;   thereby forming a multi-scale block copolymer coating.   
     
     
         2 . The method of  claim 1 , wherein the substrate is homogeneous. 
     
     
         3 . The method of  claim 1  or  2 , wherein the substrate is planar or non-planar. 
     
     
         4 . The method of any one of  claims 1 - 3 , wherein the substrate is selected from the group consisting of silicon, glass, plastic, quartz, woven or non-woven fabric, paper, ceramic, nylon, carbon, polyester, polyurethane, polyanhydride, polyorthoester, polyacrylonitrile, polyphenazine, polyisoprene, synthetic rubber, polytetrafluoroethylene, polyethylene terephthalate, acrylate polymer, chlorinated rubber, fluoropolymer, polyamide resin, vinyl resin, expanded polytetrafluoroethylene, low density polyethylene, high density polyethylene, and polypropylene. 
     
     
         5 . The method of  claim 4 , wherein the substrate is further coated with a layer of SiO 2 . 
     
     
         6 . The method of any one of  claims 1 - 4 , wherein the substrate is silicon or glass. 
     
     
         7 . The method of any one of  claims 1 - 4 , wherein the substrate is glass. 
     
     
         8 . The method of any one of  claims 1 - 7 , wherein the substrate is optically transparent. 
     
     
         9 . The method of any one of  claims 1 - 8 , wherein the first or second block copolymer is optically transparent. 
     
     
         10 . The method of any one of  claims 1 - 9 , wherein the first or second block copolymer is a strongly segregating block copolymer. 
     
     
         11 . The method of any one of  claims 1 - 10 , wherein the first or second block copolymer is a lamellae-forming block copolymer. 
     
     
         12 . The method of any one of  claims 1 - 11 , wherein the first or second block copolymer is a cylinder-forming block copolymer. 
     
     
         13 . The method of any one of  claims 1 - 12 , wherein the first or second block copolymer is poly(styrene-block-dimethylsiloxane) (PDMS). 
     
     
         14 . The method of any one of  claims 1 - 13 , wherein the first and second block copolymer are poly(styrene-block-dimethylsiloxane). 
     
     
         15 . The method of any one of  claims 1 - 14 , wherein the first block copolymer has a higher average molecular weight than the second block copolymer. 
     
     
         16 . The method of any one of  claims 1 - 15 , wherein the first block copolymer has an average molecular weight of about 100 kg/mol to about 150 kg/mol. 
     
     
         17 . The method of any one of  claims 1 - 16 , wherein the second block copolymer has an average molecular weight of about 35 kg/mol to about 65 kg/mol. 
     
     
         18 . The method of any one of  claims 1 - 17 , wherein the etching is a reactive ion etching. 
     
     
         19 . The method of  claim 18 , wherein the reactive ion etching uses a gas mixture comprising fluorine or a gas mixture comprising oxygen. 
     
     
         20 . The method of any one of  claims 1 - 17 , wherein the etching is a plasma etching. 
     
     
         21 . The method of  claim 20 , wherein the plasma etching uses a gas mixture comprising oxygen. 
     
     
         22 . The method of any one of  claims 1 - 21 , further comprising a third block copolymer. 
     
     
         23 . The method of any one of  claims 1 - 22 , wherein the second block copolymer has a higher average molecular weight than the third block copolymer. 
     
     
         24 . The method of any one of  claims 1 - 23 , wherein the third block copolymer has an average molecular weight of about 5 kg/mol to about 25 kg/mol. 
     
     
         25 . The method of any one of  claims 1 - 24 , including step (h). 
     
     
         26 . The method of any one of  claims 1 - 25 , wherein the passivating of step (i) is with a polymer brush or a silane. 
     
     
         27 . The method of  claim 26 , wherein the polymer brush is a PDMS brush. 
     
     
         28 . The method of  claim 26 , wherein the silane is a perfluorosilane. 
     
     
         29 . The method of any one of  claims 1 - 28 , wherein the advancing water contact angle of the coating is greater than about 90°. 
     
     
         30 . The method of any one of  claims 1 - 29 , wherein the receding water contact angle of the coating is greater than about 90°. 
     
     
         31 . The method of any one of  claims 1 - 30 , wherein the WCA hysteresis of the coating is less than about 10°. 
     
     
         32 . The method of any one of  claims 1 - 31 , wherein the coating has a RMS roughness of greater than about 40 nm. 
     
     
         33 . An article comprising a surface and a polymer coating on said surface; wherein the polymer coating is poly(styrene-block-dimethylsiloxane). 
     
     
         34 . An article comprising a surface and a polymer coating on said surface; wherein the polymer coating is a block copolymer comprising a plurality of styrene monomers and a plurality of dimethylsiloxane monomers. 
     
     
         35 . The article of  claim 33  or  34 , wherein the surface is optically transparent. 
     
     
         36 . The article of  claim 33  or  34 , wherein the polymer coating comprises a first block copolymer and a second block copolymer. 
     
     
         37 . The article of  claim 36 , wherein the second block copolymer is and poly(styrene-block-dimethylsiloxane). 
     
     
         38 . The article of  claim 36 , wherein the second block copolymer comprises a plurality of styrene monomers and a plurality of dimethylsiloxane monomers. 
     
     
         39 . The article of any one of  claims 36 - 38 , wherein the first block copolymer has a higher average molecular weight than the second block copolymer. 
     
     
         40 . The article of any one of  claims 36 - 39 , wherein the first block copolymer has an average molecular weight of about 100 kg/mol to about 150 kg/mol. 
     
     
         41 . The article of any one of  claims 36 - 40 , wherein the second block copolymer has an average molecular weight of about 35 kg/mol to about 65 kg/mol. 
     
     
         42 . The article of any one of  claims 36 - 41 , further comprising a third block copolymer. 
     
     
         43 . The article of  claim 42 , wherein the second block copolymer has a higher average molecular weight than the third block copolymer. 
     
     
         44 . The article of  claim 42  or  43 , wherein the third block copolymer has an average molecular weight of about 5 kg/mol to about 25 kg/mol. 
     
     
         45 . The article of any one of  claims 33 - 44 , where the polymer coating further comprises a perfluorosilane. 
     
     
         46 . The article of any one of  claims 33 - 45 , wherein the advancing water contact angle of the coating is greater than about 90°. 
     
     
         47 . The article of any one of  claims 33 - 46 , wherein the receding water contact angle of the coating is greater than about 90°. 
     
     
         48 . The article of any one of  claims 33 - 47 , wherein the WCA hysteresis of the coating is less than about 10°. 
     
     
         49 . The article of any one of  claims 33 - 48 , wherein the coating has a RMS roughness of greater than about 40 nm. 
     
     
         50 . A method of repelling water, comprising exposing to water a surface of an article of any one of  claims 33 - 49 .

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